US7396446B2 - Magnesium anodisation methods - Google Patents

Magnesium anodisation methods Download PDF

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US7396446B2
US7396446B2 US10/486,696 US48669604A US7396446B2 US 7396446 B2 US7396446 B2 US 7396446B2 US 48669604 A US48669604 A US 48669604A US 7396446 B2 US7396446 B2 US 7396446B2
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magnesium material
phosphate
magnesium
acid
electrolyte
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US20040238368A1 (en
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Ian Grant Mawston
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Keronite International Ltd
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Keronite International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/30—Anodisation of magnesium or alloys based thereon

Definitions

  • magnesium relates to magnesium anodising systems and methods.
  • the terms “magnesium”, “magnesium metal” and “magnesium material”, may be used interchangeably, and are all to be understood to refer to or include magnesium metal and/or magnesium alloy(s) and/or mixtures thereof, and/or any articles or compounds comprising or including magnesium.
  • Magnesium is a very light, yet strong metal and is finding increasing acceptance for metal die castings, particularly where weight savings are desired.
  • its property of shielding electromagnetic radiation is causing it to be of interest as a replacement for plastics in applications such as computers and mobile telephones.
  • it is a reactive metal and corrosion, whether general or by galvanic effects, is a major problem.
  • the anodisation of aluminium and its alloys is often conducted in sulphuric acid in which the oxide layer formed is slightly soluble.
  • the rate of build decreases, so ultimately there is an equilibrium point at which the rate of dissolution is equal to that of further film growth.
  • the dissolution of the film causes the formation of pores through which the ionic migration necessary to the electrochemical oxidation of the metal takes place. Without these pores only very thin films would be possible. After the electrochemical oxidation process is complete, the pores are scaled. Sealing of anodised aluminium can be achieved with hot water or simple inorganic chemical solutions.
  • anodising magnesium relies on this property to create a rough, very porous layer which may form a base for paint or other surface coatings to be applied afterwards.
  • an anodic film may be formed in an electrolyte of high pH, containing alkali hydroxides. The process proceeds by means of sparking, which sparking forms a sintered ceramic oxide film as the metal substrate is coated.
  • PCT/NZ96/00016 (WO 96/28591) (Barton) there is disclosed a viable procedure for anodising magnesium or magnesium alloys. It involves anodising the material in an ammonia containing electrolyte solution. The presence of some phosphate compounds in the solution is also disclosed. Enhancements of such a Barton procedure are disclosed in PCT/NZ98/00040 (WO98/42892) (MacCulloch et al).
  • a method of anodising magnesium material which includes anodising the magnesium material while it is immersed in an aqueous electrolyte solution having a pH above 7 and in the presence of a phosphate, the electrolyte solution also containing a sequestering agent.
  • phosphate is an alkali metal phosphate.
  • the electrolyte solutions contains an alkali metal hydroxide.
  • the electrolyte further includes a plasma suppressing substance.
  • the electrolyte further includes an amine.
  • the sequestering agent is in the form of ethylene diamine tetramethylene phosphonic acid.
  • the current passed through the electrolyte solution is a pulsed DC current.
  • anodizing magnesium material substantially as described above, wherein the anodizing of the magnesium material follows a pre-treatment designed to prepare the magnesium material for anodization.
  • the pre-treatment includes one or more of the following sub-steps:
  • the cleaning step includes an immersion of the magnesium material into a solution containing caustic soda.
  • the etching step includes an immersion of the magnesium material into a solution containing at least one acid.
  • the etching step includes an immersion of the magnesium material into a solution containing DEOXALUME®
  • the surface activation step includes an immersion of the magnesium material into a solution containing a source of fluoride ions.
  • the surface activation step includes an immersion of the magnesium material into a solution containing a source of fluoride ions and an acid.
  • the surface activation step includes an immersion of the magnesium material into a solution containing potassium fluoride and nitric acid or phosphoric acid.
  • the surface activation step includes an immersion of the magnesium material into a solution containing ammonium bifluoride.
  • the surface activation step includes an immersion of the magnesium material into a solution containing DEOXALUME®.
  • the at least one pre-treatment steps described above as (a), (b), (c) may be undertaken in any order and/or may be repeated as required or as desired, or as dictated by the condition of the magnesium material to be pre-treated and subsequently anodized. Furthermore, and again depending upon the condition of the magnesium material, only one or two (or three) of the pretreatment sub-steps may be utilized.
  • the cleaning step may be followed by the etching step, and subsequently followed by the surface activation step.
  • the cleaning step may involve the immersion of the magnesium material into an appropriate cleaning solution.
  • the cleaning step may involve the immersion of the magnesium material into a solution which includes caustic soda. Any suitable concentration may be utilized as required or as desired, or as dictated by the condition of the magnesium material to be cleaned.
  • the caustic soda may include sodium hydroxide at a concentration of between 10-50% w/v. A concentration of approximately 30% w/v may be particularly suitable.
  • the magnesium material may be immersed in the cleaning solution for any length of time, as required or as desired, or as dictated by the condition of the magnesium material.
  • the immersion time may be between 2-12 minutes, with approximately 5 minutes being particularly suitable.
  • the caustic soda solution may be at any suitable temperature, as required or as desired, or as dictated by the condition of the magnesium material.
  • the solution may be at a temperature of between 50-95° C., with a range of 70-85° C. being particularly suitable.
  • the magnesium material may be rinsed, and preferably with water.
  • De-ionized water may be particularly suitable.
  • the etching step may preferably include the immersion of the magnesium material into a solution containing at least one acid.
  • Any suitable acid or acids may be utilized as required or as desired. Examples include nitric acid and phosphoric acid.
  • any suitable concentrations of acid may be utilized as required or as desired.
  • the acid used is nitric acid, it may preferablybe of a concentration of approximately 0.4-0.8 M, with a particularly suitable range being 0.5-0.6 M.
  • the magnesium material may be immersed into a solution containing DEOXALUME®. which is a proprietary product manufactured by Henkel Corporation. If DEOXALUME®. is used, it may preferably be diluted to, approximately a 10% concentration.
  • the etching step serves to remove surface layers of the magnesium material which assists in the anodization process.
  • the magnesium material may be immersed in the etching solution for any length of time, as required or as desired or as dictated by the state of the magnesium material. For example, if phosphoric acid or nitric acid were to be used a time of approximately 30 seconds to 4 minutes may be suitable. If DEOXALUME® is used, a time of approximately 10-30 seconds may be suitable.
  • the temperature of the etching solution may be in the range of 10-80° C., with a range of approximately 20-40° C. being particularly suitable.
  • the magnesium material may be rinsed after the etching step, and preferably with water.
  • De-ionized water may be particularly suitable.
  • a further cleaning step may be undertaken after the etching step, and preferably a further rinsing of the magnesium material, for example with de-ionized water, may follow the second cleaning step.
  • phosphate is understood to include or refer to, collectively or singularly, either a phosphate or a source of phosphate ions.
  • TEA is understood to refer to the tertiary amine Tri-ethanolamine.
  • the method of anodising magnesium material may include the step of anodising the magnesium material while it is immersed in an aqueous electrolyte solution having a pH above 7, and in the presence of a phosphate and a sequestering agent.
  • the phosphate may include an ortho-phosphate and/or a pyro-phosphate.
  • any suitable source of phosphate may be utilised in the solution.
  • an alkali metal phosphate such as sodium dihydrogen ortho phosphate.
  • the phosphate may be provided by a phosphoric acid, or salt thereof.
  • phosphate concentrations may be utilised as required or as desired, and experimental trial and error will enable the optimum or desired range of concentration to be ascertained.
  • concentrations of the order of 0.02M to 0.1M may be particularly suitable. It Is to be understood and appreciated that this range is given by way of example only, and concentrations of phosphate outside this range is also within the scope of the present invention.
  • the pH may preferably be greater than 9, and, more specifically, a pH in the range of 10.2-11+ is found to be particularly suitable.
  • the electrolyte solution may be provided with a source of hydroxide ions, for example an alkali metal hydroxide such as KOH or NaOH.
  • a source of hydroxide ions for example an alkali metal hydroxide such as KOH or NaOH.
  • Any suitable concentrations of base may be utilised as required in order to reach a preferred or desired pH.
  • the electrolyte solutions may also include a plasma suppressing substance.
  • the role of the plasma suppressing substance is primarily to reduce the tendency for plasma discharges to form at defect sites on articles being anodised.
  • An example of a suitable plasma suppressing substance may be an acrylic modification of maelic acid.
  • a further example is the product P80.RTM., which is a compound manufactured by Cyanamid Corporation of the United States and which is a copolymer of allyl sulfonic acid and maleic anhydride, that is to say a polyacrylamide, as disclosed, for example in, U.S. Pat. No. 4,810,405 to Waller, et al. issued on Mar. 7, 1989, entitled Rust removal and composition thereof, and U.S. Pat. No. 5,062,962 to Brown et al. issued on Nov. 5, 1991, and entitled Methods of controlling scale formation in aqueous systems.
  • any suitable amounts or concentrations of the plasma suppressing substance may be utilised as required or as desired.
  • a concentration in the range of 100 to 400 ppm may be suitable, although concentrations of the plasma suppressing substance outside of this range are also within the scope of the present invention.
  • the electrolyte solution may preferably include a sequestering agent.
  • a sequestering agent One role of the sequestering agent is to bind any loose or superfluous ions (usually metal ions) so that they cannot react and, for example, form white powder deposits and the like.
  • Any suitable sequestering agent ma)y be utilised, for example ethylene diamine tetramethylene phosphonic acid or DEQUEST® 2066 manufactured by Henkel Inc of the United States. Any suitable concentration range may be utilised and this may be determined by trial and experimentation. However, a concentration range of the order of 0.002M to 0.02M may be particularly suitable. Concentrations outside of this range are however also deemed to be within the scope of the present invention.
  • the electrolyte solution may also preferably include an amine, and more particularly a secondary or tertiary amine.
  • TEA is particularly suitable as it appears to work with the sequestering agent to produce the surprising result referred to previously.
  • the concentration of the TEA may be any required or desired level, although a concentration in the range of 40-150 g/l may be particularly suitable. Again, a concentration outside of this range is also considered to be within the scope of the present invention.
  • the voltage applied to the electrolyte solutions may preferably be a direct current (DC). It is found that either a pulsed or a DC current may be suitable for use with the methods of the present invention. However, when the electrolyte solutions contains both an amine such as TEA and a sequestering agent such as DEQUEST® 2066 it is found that the anodisation of the magnesium material proceeds quite satisfactorily with just the use of straight DC current. This is of advantage and of commercial significance as a straight DC current does not require the use of expensive and/or specialised rectifiers and the like which are required to produce a pulsed current.
  • DC direct current
  • the magnesium material may be pre-treated and or cleaned prior to the anodising of same. Any suitable pretreatment and/or cleaning of the magnesium material may be utilised as required or as desired, or as dictated by the condition or state of the magnesium material.
  • the anodising of the magnesium material may follow one or more of the pre-treatment steps described in WO 02/28838 A2.
  • TEA and/or the sequestering agent allows less intensive pre-treatment or cleaning steps to be undertaken in order to prepare the magnesium material satisfactorily for the anodising process.
  • the anodic reaction takes place in a vessel in which the article to be anodised is connected to an electrically-conductive rack and immersed in the electrolyte.
  • the rack will be coated in plastic except for small contact areas where it forms an electrical connection to the article being anodised.
  • the rack is composed of a material that will passivate under the electrical conditions of tile anodising process, it is not necessary to coat the rack with an insulator, but it may be desirable to do so for improved efficiency.
  • the vessel containing the electrolyte and the article to be anodised to be made of insulating plastic, provided that electrically conductive counter-electrodes are inserted in the tank, most commonly in the sides. It is desirable that these be inert chemically, preferably of stainless steel, type 316. Although it is possible to use counter-electrodes composed of alternative substances, for example, aluminium, this is undesirable since in another modification of the process, a reverse polarity voltage is applied to the article resulting in a brief, anodic polarisation. Stainless steel has the advantage of being inert under these conditions whereas aluminium would anodise, preventing the proper functioning of the standard cycle.
  • the electrolyte is operable over a broad temperature range, from around zero to its boiling point, but the process operates optimally over a range 20-60° C.
  • the voltage applied to the electrolyte is normally direct current.
  • the output produced by a rectified three phase power supply, comprising a voltage of constant polarity fluctuating by approximately 5% is suitable, as is smoothed DC.
  • Modified waveforms, for instance, pulsed or superimposed AC voltages may also be employed although these result in different film thickness and other characteristics than that normally obtained from direct current anodisation.
  • anodic voltage When an anodic voltage is first applied to the article to be anodised the electrical resistance is low but this progressively increases as an insulating anodic film forms on the surface. The result is an increasing voltage when anodising current is held constant.
  • the process is normally controlled by means of a constant current, preferably in the range 50 A/m 2 to 500 A/m 2 and optimally around 200 A/m 2 .
  • the imposed voltage When operated at 200 A/m 2 , the imposed voltage may be expected to reach 200 volts after two to three minutes, and for a commercially-useful coating, the voltage may reach an ultimate limit of 230 to 270 volts. Very thin films, suitable for some applications may be achieved using lower voltages. The film continues to build if the voltage is held constant on attaining a certain limit, for example, 220 volts, and as this takes place, the current dwindles.
  • a brief cathodic voltage may be applied to the article prior to anodisation. This is usually current controlled and results in a relatively low voltage, typically less than 20 volts, and considerable gassing from the article in the electrolyte. Such a cathodic cycle is not known to influence the chemical composition of the surface of the article to be anodised, but may assist with preparation of a clean and uniform surface for anodisation.
  • the anodising electrolyte has efficient circulation both for reasons of maintaining uniform electrolyte composition and heat removal. Stagnant flow may be minimized by the use of ultrasonic cleaning devices during anodisation.
  • the use of ultrasonic cleaning during anodisation results in a clean, smooth anodic film. It appears that ultrasonic energy reduces the boundary layer on the surface of the forming film and improves ionic transfer to the bulk electrolyte. There is an additional benefit in that loosely adherent particles, for example, inclusions in die cast components, are removed more readily.
  • Ultrasound use is not limited to the anodising electrolyte, and may also be used to improve rinse or cleaning process efficiency. However, the application of ultrasound to cleaning processes is well established in such processes.
  • a composite coating comprising many layers features many potential problems, including the expense of several processing stages and the accumulated probability of failure from each of those steps. Plainly it is desirable to achieve the final result in as few steps as possible. Since the overall production rate is determined by the cycle time of the slowest process, time savings in processing lead to efficiency gains overall.
  • a common problem encountered in anodising magnesium articles arises from the fact that many magnesium articles are die cast rather than extruded, forged or rolled. Die-castings frequently manifest a range of defects. These include porosity, cracks, flow lines, inclusions, plaques of externally solidified material and others. As a tool steel die ages defects arise from tool wear. Die-casting alloys are frequently heterogeneous, unlike the homogeneous solid solutions that are frequently used for extrusion.
  • the electrolyte solution may include a buffering agent to maintain the pH and the desired level or range.
  • a buffering agent may be utilised, although a tetra-borate may be particularly suitable.
  • an alkali metal tetraborate such as sodium tetraborate may be particularly suitable.
  • Phosphoric acid 75% 100 g/L Triethanolamine 99% 85 g/L Potassium Hydroxide solution 45% 210 g/L (pH 11.2) Conductivity 70 mS at 20° C.
  • Phosphoric acid 85% 90 g/L Triethanolamine 99% 90 g/L Dequest 2066 2 g/L Sodium Hydroxide To achieve pH 11.0 Conductivity 75 mS at 20° C.
  • Anodising was carried out at 300 A/m 2 at 45° C. using filtered DC for 2 min.
  • the average voltage was 70 Volts with an end voltage of 155 Volt.
  • the deposited anodic layer was a light grey and had a thickness of 10 um.
  • Triethanolamine is a preferred tertiary amine as it is odourless, has good solubility, a high boiling point, and a satisfactory dissociation constant.
  • a high viscosity anodising solution is beneficial to film formation especially if this results from the employment of high molecular weight substituted tertiary or secondary amines.
  • An example was the use of 75 g/L of 1-di-ethyl amino 2-propanol. The films produced were easily formed at low average voltage and at good current efficiency.
  • pre-treatnielt scheme was applied to both AZ91 and AM50 alloys and was found to be beneficial in obtaining good polarnsation and an even coating.
  • Coating thickness and porosity can. to some degree, be controlled by choosing various combinations of both current density and time. For example, a high current density for a short time will produce a less porous film than a lower current density for a longer time given that the film thickness is the same in both cases.
  • the ratio of peak current to average current can be as high as 10:1. This could be disadvantageous in some cases as the power supply must be over-designed for relatively small average currents.
  • Potassium hydroxide is the preferred alkali.
  • a lower electrolyte pH in combination with the phosphonate additive was found to be beneficial in promoting anodic film formation on substrates that had had high aluminium content due to segregation. This was particularly so if fluoride pre-treatment was used.
  • the magnesium material may instead be pre-treated.
  • the pre-treatment preferably includes the following steps, namely a cleaning step, an etching step, and a surface activation step.
  • the magnesium material is first subjected to a cleaning step followed by the etching step, followed by a further cleaning step, and followed lastly by a surface activation step.
  • a rinsing step involving the rinsing of the magnesium material with de-ionized water. This pre-treatment process is summarized in FIG. 2.
US10/486,696 2001-08-14 2002-08-14 Magnesium anodisation methods Expired - Lifetime US7396446B2 (en)

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NZ51270101 2001-08-14
NZ512701 2001-08-14
PCT/NZ2002/000156 WO2003016596A1 (en) 2001-08-14 2002-08-14 Magnesium anodisation system and methods

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JP (1) JP4417106B2 (zh)
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EP3368706A4 (en) 2015-10-27 2019-05-01 Métal Protection Lenoli Inc. ELECTROLYTIC METHOD AND APPARATUS FOR SURFACE TREATMENT OF NON-FERROUS METALS
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AU2002334458B2 (en) 2008-04-17
JP4417106B2 (ja) 2010-02-17
US20040238368A1 (en) 2004-12-02
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